Synthesis, Assembly And Gelation Of Novel Functional Materials With Triazine Moieties

Because of triazine ring’s conjugated system, it’s prone to occur nucleophilic substitut ion reaction. Especially the product with amine derivatives is widely us ed in assembly syste m to reinforce the aggregates. Therefore it has significant application value and applicat ion va lue to prepare nove l organical funct iona l materia l w ith triazine ring, napht hale ne and peryle ne diimides derivat ives in d ifferent ways. Therefore, three kinds of compounds w ith tria zine ring were synthes ized to invest igate the assembly perfor mance and gel properties respective ly. Also the stacking structure of aggregates and the effects of solve nts on ge l properties were also discussed. The details are summarized as follows:1. Four target naphtha limide derivat ives N1-N 4 were synthes ized fro m 1, 4, 5, 8-Naphtha lenetetracarboxylic dianhydr ide and tria zine derivative. The four compounds were assembled with perylene diimides(C ompound H). Photo-phys ical properties was studied in low concentration, and assembly behavior was investigated in higher concentration. The results show that in low concentrat ion the UV- vis ib le absorption spectrum and fluorescence emiss ion spectra of fo ur assemb ly syste ms exhibit d ifferent response behaviors as the content of naphtha limide derivatives increasing. Also increasing of the content of naphtha limide derivat ives contrib uted to fluorescence quenching of compound H. In higher concentration assembly process can happen effectively in d ichlorometha ne solut ion. It is proved that napht halimide derivatives and compound H were combined with triple hydrogen bonding and π-π interactions, and the direction of π-π interactions is vertical to the growth direction of assembly.2. Four new ge lators 1- 4 with b is- amide- me la mine motifs were synt hesized from me lamine derivatives with a mino group and dicarboxylic acids by using EDC and HO Bt as coupling agents. Based on ge lation experiment, sol- gel ge latio n temperatures can be enhanced wit h longer alkyl cha in, and present S- type curve w ith gel concentration increasing. By introduc ing the Hansen solub ility parameters, we found that the stable sol- gel trans it ion te mperature was related to the solubilit y parameters δd and δp, and showed a negat ive correlatio n w ith t he m. In addit io n, the macro- morphology of ge l is switc hed by the hydrogen-bonding Hansen solub ility parameter δh. Solvents with δh <5.7MPa1/2 could produce transparent gels, opaque gel formed in solvents w ith 5.7MPa1/2 < δh < 7.4MPa1/2 and precipitation occurred if δh is larger than 7.4MPa1 /2. The SEM investigatio n suggested that the gel fibers in MC H and tolue ne were intertw isted by thinner fiber with dia meters less than 25 nm and in ethyl acetate a three-dime nsio nal collection of intertw isted and inter locked fibers with diameters from 50 to 100 nm.3. Three naphtha limide gelators N 26 M, N 62 M and N 66 M were synt hesized from gelat ion of napht halimide derivative by using EDC and HO Bt as coupling agents. Assemb ly capability decreased significantly by assemb ly experiment, for the crystal structure can’t be formed effectively. According to gelation experiment, gelling ability increases with t he r ise of cha in length between amide and naphtha limide mo ieties, while the gel performa nce increases wit h the rise of le ngt h between amide and triazine mo ieties. Sol- gel ge lat ion temperatures and the macro- morphology of ge l are also affected by the Hansen solub ility pa rameters. The stable sol- gel transit ion te mperature was related to the solubility parameters δd and the macro-morphology was related to δh.The results a ll above showed that, as an excellent donor for trip le hydrogen bonding, tria zine mo ieties could promote assembly process effective ly. These studies established experimenta l basis and theoretical basis for furt her exploration of the assembly perfor mance and environmenta lly responsive of compounds w ith triazine- naphthalimide groups.